Anthraquinone vat dyestuffs



Patented Aug. 24, 1948 ANTHRAoUrNoNE VAT'DSFESTUFFS- Francis Irving and'-Alistair Manchester,

Livingston, Blackley,

England, assignors" to Imperial Chemical Industries Limited; a corporation of GreatBritain.

No Drawing" No. 702,092.

Application In Great Britain October oetobere; 1946, Serial.

" 2 Claims. (01. 2601-368).

This invention relates to new vat dyestuffs and more particularly it relates to new reddishviolet vat dyestuffs of the anthraquinone series.

In U. S. Patent 1,539,689 it hasalready been proposed to manufacture-vat dyestuffs by condensing together an aminoanthraquinone, or 'a derivativethereof and a l-aminoanthraquinone- 2-carboxylic acid or its chloride.

In the previously described process it'has not been proposed-'to use} as'' aminoanthraquinone, 5-- amino e1 wia'diaroylamino anthraquinones.

We have now found that when in the above process there is used;- as aminoanthraquinone, 5.-amino1;4ediaroylaminoanthraquinone there are obtained vat dyestuffs which-dye cotton in Bordeaux shades of greaterrbrilliance and tinctorial power than those of similar shade described in theatorementioned specification. 1

Accordingly our invention :provides a: .process fonthelmanufacture of new.-yat;dyestuffs which comprises acylating a fi-amino -ia lediaroylamino anthraquinone ,with an acylating,., derivative of an anthraquinone 2 carboxylic acid which carries in the 1-position an-aminogroup or anatom or group readily .convertiblethereto. l

Thenewidyestufis are thusicompoundswor the formula QC O\ NH X 00 oo where R1 and R2 are aryl groups and X is an amino group or an atom or group readily convertible thereto.

As -amino- 1 4-diaroylaminoanthraquinones there may be used for example 5-amino-1z4- dibenzoylaminoanthraquinone, B-aminol 4- dip-methanesulphonylbenzoylaminoanthraquinone, 5 amino 1:4 dianisylaminoanthraquinone, 5-amino -l:4 di p toluylaminoanthraquinone, 5 amino 1:4 di-m-methanesulphonylbenzoylaminoanthraquinone and 5-amino-1z4-di-pchlorobenzoylaminoanthraquinone.

These substances may be made by the method described in British speci cation No. 421,591.

As anthraquinone Z-carboxylic acids there may NHCOR1 NHCOR:

be usedyfor example"1-nitroanthraquinone-2 carboxylicacid; 1-aminoanthraquinone-2-carboxylic acid and 1 chloroanthraquinone-2- car-. boxylic acid, and as acylating derivatives thereofthere may be used for example th acid chlorides;

It is a further featuraof the invention, when thew anthraquinone-2-carboxylic I acid contains, not-- an. amino-,group but a groupreadily .cone. vertible-thereto, to convert the ,said group to an amino group after the acylation step. This may be eriected-by known processes, Thus when the saidygroup is a nitro group it may be reduced to-.an;-amino.group. It is notalways necessary tQUbI'iRQ' E-IbQUbthiS change separately sincethe vattingprocess commonly-effects this reduction. Besidesareduction the ,nitro group may be converted into an amino group by treatment with ammoniaas alsoumay a chlorine or bromine atom As. said alreadythe new dyestuffs dye .cotton in -Bordeaux shades. They also dyeviscose and naturalrsi-lk.inn-similar shades. The dyeings, are characterised by great brilliance and tinctorial power. They-are also remarkablyiast to. wet treatments and. to light.

Theflnvention. is illustrated but not limited by the following examples in which parts are by weight:

Example 1 A mixture of 23 parts of 5-amino-1z4-dibenzoylaminoanthraquinone, 18 parts of l-nitroanthraquinone-Z-carboxylic acid chloride and 400 parts of dry nitrobenzene is heated at C. for 2-3 hours. The mixture is then cooled, filtered and washed with benzene and then with ethanol. It is then dried. The 1:4-dibenZ0ylamino-5-(1- nitroanthraquinone -2- carboxylamino) anthraquinone so obtained dyes vegetable fibres in strong Bordeaux shades from a deep red-brown caustic soda-sodium hydrosulphite vat, the dyeings being fast to boiling with alkali and to chlorine.

If desired, the nitro group in the above product may be converted to an amino group before the product is used as a dyestufi. This can be done for example by heating a suspension of the nitrocompound in 10 parts of nitrobenzene at C. and passing ammonia gas through the mixture, for 2-3 hours. Alternatively the amine compound may be obtained by heating a mixture of 92 parts of S-amino-l:4-dibenZ0y1amin0- anthraquinone, 65 parts of l-aminoanthraquinone-2-carboxylic acid chloride and 1200 parts of dry nitrobenzene for 3 hours at 190 C. The lze-dibenzoylamino 5 -(1-aminoanthraquinone- *Z-barbdiiy'lamino) -anthraquinone is isolated by filtration at 60 C. and washing first with nitrobenzene, then with benzene and then finally with ethanol. It dissolves in concentrated sulphuric acid to give a clear green solution.

Example 2 nitrobenzene and .the suspension is heated at Y 185-190 C. for 90 minutes while a stream of am monia is passed through it. tained is cooled and the solid which separates is filtered off, washed with ethanol and dried. It-

dissolves in concentrated sulphuric acid to give a red-brown solution and it dyes vegetable fibres from an olive-green vat in bright red-violet shades.

Example 3 A mixture of 98 parts of 5-amino-1z4-di-ptcluylaminoanthraquinone, '70 parts of l-nitrm anthnaquinone-2-carboxylic acid chloride and 1400 parts of dry 180 C. for 8 hours. The product is filtered 01f, Washed with o-dichlorobenzene, benzene and then ethanol and dried. It dissolves in concentrated sulphuric acid to give a yellow-green solution and dyes cotton in shades which are very slightly yellower than those given by the dyestufi described in Example 1.

In a similar manner, dyestufis with closely similar dyeing properties may be prepared from 5-amino-1:4-dianisylamino-, 5-amino -1:4- di p chlorobenzoylamino-, and 5-amino-1:4=-dim methanesulphonylbenzoylamino-anthraquinones. These intermediates are prepared by acylating 5-nitro-1z-diaminoanthraquinone with .the corresponding acid chlorides in a solvent such as o-dichlorobenzene at about 140 0., and then at 180 C. for about o-dichlorobenzene is stirred at a reducing the nitro group by means of sodium sulphide or sodium hydrosulphite.

We claim:

1. The vat dyes of the formula:

0 NH-C 0-642 0 I u moo-N113 NH-COOR' wherein R and R stand group consisting of H, CH3 and wherein X of the group consisting 2. The vat dye of for substituents of the SO2CH3, OCH3, and stands for a substituent of -NO2 and -NH2. the formula:

I 0 mucoam NH-cog NH2 FRANCIS IRVING.

ALISTAIR LIVINGSTON. REFERENCES CITED The following references are of record in the file of this patent: v

UNT'I'ED STATES PATENTS Number -Name Date 1,539,689 Nawiasky et a1 May 26, 1925 2,179,552 Graham Nov. 14, 1939 2,346,726 Buxbaum Apr. 18, 1944 FOREIGN PATENTS Number Country Date 465,769 Great'Britain May 14, 1937 542,801 Germany Feb. 3, 1932 

